Design Of Catalysts Research Articles

Modulating structure of Ce-UiO-66 by introducing fluorinated terephthalic acid for enhanced removal efficiency of antibiotics: Insights into degradation kinetics and pathways

In this work, the 2-fluoroterephthalic acid with asymmetric structure and high electronegative F species was introduced in the assembly of Ce-UiO-66 catalysts to increase the defect density and enlarge pore structure for enhancement in removal efficiency of sulfamethoxazole. Owing to the strong coordination ability from high electronegative F species of 2-fluoroterephthalic acid with Ce-oxo nodes, the designed CUF exhibited improved interfacial properties (accelerated electron transfer rate, available active sites and enhanced interaction with PMS), which was favorable for the exploration and accessibility of active sites with sulfamethoxazole and PMS to decrease the adsorption barrier and accelerate PMS activation. As a result, the CUF catalysts exhibited higher adsorption capacity (173.4 mg/g) than that of CUH (117.8 mg/g), the enhanced degradation efficiency of sulfamethoxazole with a rate constant higher than 2.3 times CUH, good elimination (>95 %) of methylene blue, tetracycline and ibuprofen. In addition, the CUF/PMS system possessed satisfactory stability in wide solution pH, recycling and real water and good potential application in continuous wastewater treatment based on the designed dynamic catalytic reactor. This work provided deep insight into the design of catalysts with high adsorption performance and degradation efficiency based on the structure–activity relationship.

Kinetics of continuously catalyzed peroxymonosulfate in a fixed-bed reactor

Most studies have been conducted in batch reactors. Therefore, understanding the catalytic reaction kinetics and mass transfer in continuous catalytic reactors is essential for the design of heterogeneous catalysts and optimisation of catalytic degradation processes in heterogeneous systems. In this research, granular catalysts (Co-600/AlSi-0.25/AP) is used to investigate the kinetic constants and mass transfer resistance for the continuous catalytic decomposition of peroxymonosulfate (PMS) and degradation of p-nitrophenol (PNP) in a fixed bed reactor. The flow rate is 5 mL/min and reaction temperature is 30 °C, intrinsic kinetic constants of PMS decomposition and PNP degradation are 48 and 195 kg−1·min−1·L, respectively, which are 20–30 times of the apparent kinetic constants of PMS decomposition and PNP degradation in fixed bed reactors, respectively. The decomposition rates of PMS and PNP are controlled by mass transfer, and the reaction takes place in the diffusion-controlled regime. The mass transfer kinetic model based on the plug-flow model shows a good agreement between the calculated data and the experimental data. Which indicate that PMS decomposition and pollutant degradation in a fixed-bed reactor can be predicted by mass transfer kinetic modelling, guide the design of catalysts and the optimisation of heterogeneous catalytic reaction system in a fixed-bed reactor.

ZIF-8 Porous Liquids with Different Sterically Hindered Solvents and Porous Guests for Catalytic Conversion of Carbon Dioxide.

Utilizing carbon dioxide (CO2) as a raw material is an effective way to reduce carbon emissions, and developing catalytic systems with high catalytic activity and stability is crucial for the efficient utilization of CO2. Porous liquids (PLs) with both permanent pores and fluidity have great potential in the fields of catalysis, gas sorption, and storage. Nevertheless, the catalytic performance of PLs is affected by many factors; therefore, further study is needed. Herein, we proposed a general strategy to construct a series of type III PLs with different chemical structures of sterically hindered solvents and different microstructures of porous guests. Benefiting from the unique microstructures, the as-prepared PLs exhibit great potential in catalyzing the reaction of CO2 with propylene oxide under suitable conditions. Moreover, their catalytic activity exceeds that of pure sterically hindered solvents without a porous guest loading. The influences of the nucleophilicity of the anion of the sterically hindered solvent and the microstructure of the porous guests on the catalytic activity and the catalytic stability of the PLs were analyzed. Meanwhile, the mechanism of the catalytic conversion of CO2 was proposed, which is of great significance for the design and development of the subsequent PL catalysts.

Influence mechanism of divalent metals in the laminates of M2+Al-layered double hydroxides on peroxymonosulfate activation reaction pathway: Radical vs nonradical

Radical and nonradical reaction pathways have been commonly validated in peroxymonosulfate (PMS) based advanced oxidation progresses (AOPs) using layered double hydroxides (LDHs) as catalysts, but achieving efficient and selective degradation of organic pollutants remains challenging due to the unclear regulatory mechanism of laminate M2+ in PMS activation. Here, the d-orbital electrons configuration of M2+ was found to influence the degree of overlap between M−OH and O of PMS, which results in the selective dissociation of PMS to form reactive oxygen species (ROS) or achieve electron transfer pathway. Further analysis revealed that Co(II, 3d7) and Ni(II, 3d8) with filled 3d orbital electrons can serve as electron donors for PMS, leading to the cleavage of O–O bond and the efficient generation of radical-based ROS. In contrast, Mg(II, 3d0) with unfilled 3d orbital electrons and Zn(II, 3d10) with full filled 3d orbital electrons tend to act as electron shuttles, and the outermost orbitals substantially overlap with the O of PMS to form metastable complexes. Consequently, MgAl-LDH interacts with PMS to selectively degrade quinolones as electron donor through electron transfer pathway, and its performance was not inhibited by common anions and organic matter in actual water. The above results provide a basis for optimizing the design of LDH-based catalysts according to the type of laminate M2+ to achieve high selectivity and efficiency of PMS-AOPs in water purification applications.

The Reaction Mechanism and Rates at Ru Single-Atom Catalysts for Hydrogenation of Biomass BHMF to Produce BHMTHF for Renewable Polymers.

Realizing high selectivity for producing biodegradable 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF) for renewable polymers from 5-hydroxymethylfurfural (HMF) biomass through ring hydrogenation on single-atom catalysts poses a considerable challenge due to the complexity of HMF functional groups and the difficulty of H2 dissociation. We developed a detailed reaction mechanism based on ab initio molecular dynamics (AIMD) and quantum mechanics (QM) to find that Ru single-atom catalysts can simultaneously dissociate H2 and perform the ring hydrogenation of biomass-derived 2,5-bis(hydroxymethyl)furan (BHMF) to produce biodegradable BHMTHF, with a free energy barrier of 0.82 eV. The unique property of Ru single-atom sites enables H2 to dissociate easily on a single active site of Ru to participate directly in the reaction without diffusion. Furthermore, our predicted reaction rate from microkinetic analysis indicates that ring hydrogenation and side-chain hydrogenolysis are much faster than ring-opening hydrogenation over the range of 300-550 K. The product BHMTHF dominates with a selectivity of 98.9% at 300 and 78.4% at 550 K (the second product is 5-methylfurfural (5-MFA)). This study underscores the unique effectiveness of Ru single atoms in ring hydrogenation reactions using H2 as the hydrogen source, offering insights for the design of single-atom catalysts for other biomass reactions.

Mechanistic insights into the roles of copper in enhanced peroxymonosulfate activation for tetracycline degradation by copper ferrite composite catalyst

Tetracycline (TC) pollution has attracted great attention due to its wide use, non-biodegradability and potential carcinogenicity. Bimetallic catalysts/peroxymonosulfate (PMS) systems have been considered as powerful technologies for TC degradation. Although the excellent catalytic activity of copper ferrite (CuFe2O4) composite oxides for PMS has been already elucidated, the roles of increased Cu in the degradation especially from non-radical pathways are not clarified clearly. In this study, we prepared a series of CuO/CuFe2O4/Fe2O3 (CCF) catalysts to confirm the key role of molar ratios of Cu: Fe (ranging from 1:2 to 2:1) in the enhanced degradation. The optimized CCF-3 catalyst with the Cu: Fe molar ratio of 2:1 showed the best degradation efficiency up to 95.6 % and the fastest apparent degradation rate of 0.135 min−1 towards TC. In addition, the CCF-3/PMS system showed excellent adaptability and good stability in TC degradation. Importantly, a novel molecular-scale mechanism was proposed. Both radical (SO4∙-, ∙OH, O2∙ –) and non-radical (1O2, direct electron transfer) pathways were associated with the CCF-3/PMS catalytic system, where 1O2 played the dominant roles. The increased Cu significantly boosted the non-radical pathways via promoting the formation of oxygen vacancies (Ov) and its further conversion to 1O2, and facilitating electron transfer between bimetallic Cu/Fe interface. This work provides a deep insight into the formation and reaction mechanisms of non-radical species for CCF/PMS systems, and a novel foundation for the design of CuFe2O4 composite catalysts

Carbon-anchoring synthesis of Pt1Ni1@Pt/C core-shell catalysts for stable oxygen reduction reaction

Proton-exchange-membrane fuel cells demand highly efficient catalysts for the oxygen reduction reaction, and core-shell structures are known for maximizing precious metal utilization. Here, we reported a controllable “carbon defect anchoring” strategy to prepare Pt1Ni1@Pt/C core-shell nanoparticles with an average size of ~2.6 nm on an in-situ transformed defective carbon support. The strong Pt–C interaction effectively inhibits nanoparticle migration or aggregation, even after undergoing stability tests over 70,000 potential cycles, resulting in only 1.6% degradation. The stable Pt1Ni1@Pt/C catalysts have high oxygen reduction reaction mass activity and specific activity that reach 1.424 ± 0.019 A/mgPt and 1.554 ± 0.027 mA/cmPt2 at 0.9 V, respectively, attributed to the optimal compressive strain. The experimental results are generally consistent with the theoretical predictions made by our comprehensive microkinetic model which incorporates essential kinetics and thermodynamics of oxygen reduction reaction. The consistent results obtained in our study provide compelling evidence for the high accuracy and reliability of our model. This work highlights the synergy between theory-guided catalyst design and appropriate synthetic methodologies to translate the theory into practice, offering valuable insights for future catalyst development.

Rapid Surface Reconstruction of Amorphous‐Crystalline NiO for Industrial‐Scale Electrocatalytic PET Upcycling

The conversion of plastic waste into valuable chemicals through innovative and selective nano‐catalysts offers significant economic benefits and positive environmental impacts. However, our current understanding of catalyst design capable of achieving industrial‐grade current densities is limited. Herein, we develop a self‐supported amorphous‐crystalline NiO electrocatalyst for the electrocatalytic upcycling of polyethylene terephthalate (PET) into formate and hydrogen (H2) fuel. The catalyst achieves an industrial current density of over 1 A cm‐2 at 1.5 V vs. RHE, with an 80% Faradaic efficiency and a formate production rate of 7.16 mmol cm‐2 h‐1. In situ Raman spectroscopy, X‐ray absorption spectroscopy, and density functional theory calculations reveal that the rapid transformation of amorphous‐crystalline NiO into γ‐NiOOH at the amorphous‐crystalline interface provides a thermodynamic advantage for formate desorption, leading to the high activity required for industrial applications, which is difficult to achieve for fully crystalline NiO. A techno‐economic analysis indicates that recycling waste PET using this catalytic process could generate a profit of $501 per ton. This work presents a cost‐effective and highly efficient approach to promoting the sustainable utilization of waste PET.

Rapid Surface Reconstruction of Amorphous-Crystalline NiO for Industrial-Scale Electrocatalytic PET Upcycling.

The conversion of plastic waste into valuable chemicals through innovative and selective nano-catalysts offers significant economic benefits and positive environmental impacts. However, our current understanding of catalyst design capable of achieving industrial-grade current densities is limited. Herein, we develop a self-supported amorphous-crystalline NiO electrocatalyst for the electrocatalytic upcycling of polyethylene terephthalate (PET) into formate and hydrogen (H2) fuel. The catalyst achieves an industrial current density of over 1 A cm-2 at 1.5 V vs. RHE, with an 80% Faradaic efficiency and a formate production rate of 7.16 mmol cm-2 h-1. In situ Raman spectroscopy, X-ray absorption spectroscopy, and density functional theory calculations reveal that the rapid transformation of amorphous-crystalline NiO into γ-NiOOH at the amorphous-crystalline interface provides a thermodynamic advantage for formate desorption, leading to the high activity required for industrial applications, which is difficult to achieve for fully crystalline NiO. A techno-economic analysis indicates that recycling waste PET using this catalytic process could generate a profit of $501 per ton. This work presents a cost-effective and highly efficient approach to promoting the sustainable utilization of waste PET.

Aerobic Thiols Oxidative Coupling to Disulfides over Robust CoOx Nanoclusters Confined within Hierarchical Silicalite-1 Zeolite.

Disulfide is an important organic reagent and synthetic intermediate that is widely used in organic synthesis, polymers, and other fields, but its synthesis still suffers from many environmental pollution and economic problems. Here, we present an environmentally friendly and efficient base-free aerobic oxidative thiol coupling catalyzed by heterogeneous CoOx nanoclusters entrapped in hierarchical silicalite-1 zeolite, synthesized by combining silane pore expansion and metal coordination methods under hydrothermal conditions. It is confirmed that open hierarchical channels favor mass diffusion, and the chemical valence of Co species in CoOx/h-S-1-H is +2, which is different from that of Co3O4 particles in CoOx/h-S-1-I. CoOx nanoclusters, are strongly fixed in the channels of silicalite-1 zeolite via Co-O-Si bonds, which is of great importance for the high catalytic activity in both symmetrical and unsymmetrical oxidative thiol coupling reactions. After recycling experiments four times, the CoOx/h-S-1-H used has almost the same chemical state and the same distribution of Co(II) species as the fresh catalysts. Based on DFT calculations and inhibition experiments, the oxidative coupling of thiols undergoes a free radical mechanism in which Co(III) causes RS-H cleavage into RS· and H· species. Subsequently, two RS· radicals are coupled to disulfides, while H· radicals react with the O species to form H2O molecules. This work not only provides guidance on catalyst design and parameter optimization for oxidative thiol coupling but also advances the understanding of the aerobic oxidation mechanism.

Water-promoted oxidative coupling of aromatics with subnanometer palladium clusters confined in zeolites

A fundamental understanding of the active sites in working catalysts can guide the rational design of new catalysts with improved performances. In this work, we have followed the evolution of homogeneous and heterogeneous Pd catalysts under the reaction conditions for aerobic oxidative coupling of toluene for the production of 4,4′-bitolyl. We have found that subnanometer Pd clusters made with a few Pd atoms are the working active sites in both homogeneous and heterogeneous catalytic systems. Moreover, water can promote the activity of Pd clusters by nearly one-order magnitude for oxidative coupling reaction by facilitating the activation of O2. These new insights lead to the preparation of a catalyst made with Pd clusters supported on a two-dimensional zeolite, which expands the scope of the oxidative coupling of aromatics to larger substrates.

Ultra‐Narrow Alkane Product Distribution in Polyethylene Waste Hydrocracking by Zeolite Micro‐Mesopore Diffusion Optimization

AbstractPlastic pollution poses a pressing environmental challenge in modern society. Chemical catalytic conversion has emerged as a promising solution for upgrading waste plastics into valuable liquid alkanes and other high value products. However, the current methods yield mixed products with a wide carbon distribution. To address this challenge, we present a bifunctional catalytic system consisting of β zeolite mixed hierarchical Pt@Hie‐TS‐1, designed for the conversion of low‐density polyethylene (LDPE) into liquid alkanes. This system achieves a 94.0 % yield of liquid alkane, with 84.8 % of C5−C7 light alkanes. Combined with in situ FTIR and molecular dynamics simulation, the shape‐selective mechanisms is elucidated, which ensures that only olefins of the appropriate size can diffuse to the encapsulated Pt sites within the zeolite for hydrogenation, resulting in an ultra‐narrow product distribution. Furthermore, by optimizing the micro‐mesopores of Pt@Hie‐TS‐1, the scaling relationship between the pore structure and the conversion/selectivity is identified. The rapid diffusion of olefins within these micro‐mesopores significantly enhances the catalytic efficiency. Our findings contribute to the design of efficient catalysts for plastic waste valorization.

Enabling Automation of de Novo Catalyst Design: An Experimentally Validated, Multifactor Design Metric for Olefin Metathesis

Enabling Automation of de Novo Catalyst Design: An Experimentally Validated, Multifactor Design Metric for Olefin Metathesis

Unveiling the potential of aluminum-decorated 3D phosphorus graphdiyne as a catalyst for N2O reduction.

Interest in single-atom catalysts (SACs) has surged due to their potential to mitigate greenhouse N2O gas from the environment. In this study, we explore the potential of N2O reduction using porous 3D phosphorus graphdiyne decorated with an Al atom (3D-Al/PGDYN) through density functional theory. Results confirm the energetic stability of Al decorations on 3D-PGDYN and indicate that the Al atom plays an active role in catalysis. The N2O molecule undergoes spontaneous dissociation on the surface of the 3D-Al/PGDYN, initiating from the O-end, with a dissociation energy of -2.93 eV. In parallel, N2O dissociation through the N-end involves chemisorption onto the 3D-Al/PGDYN surface, with an adsorption energy (Ead) of -1.74 eV. The negative Ead values (-2.47 and -2.64 eV) indicate that CO and O2 species chemisorb onto the 3D-Al/PGDYN surface, but these energies are lower than that of N2O, suggesting that CO and O2 molecules do not hinder the N2O reduction process. Furthermore, the reaction CO + O* → CO2, which is vital for catalyst regeneration, proceeds swiftly on the 3D-Al/PGDYN catalyst with a low energy barrier of 0.11 eV, highlighting the catalyst's exceptional reactivity. This work holds significance in the design of catalysts and could be instrumental in developing new and efficient solutions for effectively removing harmful N2O from the environment.

Enhanced Stability and Selectivity in Pt@MFI Catalysts for n-Butane Dehydrogenation: The Crucial Role of Sn Promoter

The dehydrogenation of n-butane to butenes is a crucial process for producing valuable petrochemical intermediates. This study explores the role of oxyphilic metal promoters (Sn, Zn, and Ga) in enhancing the performance and stability of Pt@MFI catalysts for n-butane dehydrogenation. The presence of Sn in the catalyst inhibits the agglomeration of Pt clusters, maintaining their subnanometric particle size. PtSn@MFI exhibits superior stability and selectivity for butenes while suppressing cracking reactions, with selectivity for C1–C3 products as low as 2.1% at 550 °C compared to over 30.5% for Pt@MFI. Using a combination of high-angle annular dark-field scanning transmission electron microscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Raman spectroscopy, we examined the structural and electronic properties of the catalysts. Our findings reveal that Zn tends to consume hydroxyl groups and substitute framework sites, and Ga induces more defective sites in the zeolite structure. In contrast, the interaction between SnOx and the zeolite framework does not depend on reactions with hydroxyl groups. The incorporation of Sn significantly prevents Pt particle agglomeration, maintaining smaller Pt particle sizes and reducing coke formation compared to Zn and Ga promoters. Theoretical calculations showed that Sn increases the positive charge on Pt clusters, enhancing their interaction with the zeolite framework and reducing sintering, albeit with a slight increase in the energy barrier for C-H activation. These results underscore the dual benefits of Sn as a promoter, offering enhanced structural stability and reduced coke formation, thus paving the way for the rational design of more effective and durable catalysts for alkane dehydrogenation and other high-value chemical processes.

Characterization of Fresh, Deactivated, and Regenerated TS‐1 for Propylene Epoxidation: Investigating Surface Deactivation Species

AbstractTitanium silicalite‐1 (TS‐1) serves as an effective catalyst for propylene epoxidation in the hydrogen peroxide propylene oxide (HPPO) process, attracting wide attention from researchers and industry. Nonetheless, the TS‐1 catalyst experienced inevitable deactivation during industrial applications, which adversely impacts its lifespan. To enhance reaction stability of catalyst, the present work conducted a systematic investigation into the deactivation reason of the TS‐1 catalyst. The fresh, deactivated, and regenerated catalysts were characterized by using various analytical techniques to compare their physicochemical properties. The surface coke species of the deactivated catalysts were extracted by the Soxhlet extraction method and subsequently analyzed using GC–MS. Additionally, the pathways for by‐product formation were simulated through Gauss software. The results indicated that the so‐called coking deposits formed during the reaction predominantly consist of propylene glycol, ethers, and oligomers. These coke species covered the partial active sites on the catalyst surface, blocked the pores of the catalyst, and accordingly led to the deactivation of the catalyst, although the crystalline structure of the catalyst hardly changed after deactivation. These results provide a theoretical basis and novel insights for the rational design and development of efficient catalysts for the HPPO process.

Efficient Hydrocracking of Waste Polyethylene into Branched Liquid Fuels over Low Pt-loaded Nb2O5 Catalyst.

Catalytic hydrocracking of polyethylene to branched liquid fuels has drawn particular attention. Here, bifunctional Pt/Nb2O5 catalysts with different Pt loadings were prepared for polyethylene hydrocracking. It was found that the low-loading Pt/Nb2O5 catalysts exhibited significantly higher catalytic activity than those of high-loading Pt/Nb2O5 catalysts, with the 0.2Pt/Nb2O5 catalyst having the best catalytic performance (79.2% yield of liquid fuels (C5-C19) with branched alkanes accounting for 85.2%). Detailed characterizations revealed that the activation of H2 played a crucial role in the efficient hydrocracking of polyethylene. The 0.2Pt/Nb2O5 catalyst, with highly dispersed Pt nanoclusters on the surface, facilitated the highly active Hδ- species formation, thereby enhancing hydrocracking activity. This work highlights the importance of H2 activation in the hydrocracking of polyethylene and provides insights for the design of efficient catalysts.

Developing Practical Catalysts for High‐Current‐Density Water Electrolysis

AbstractHigh‐current‐density water electrolysis is considered a promising technology for industrial‐scale green hydrogen production, which is of significant value to energy decarbonization and numerous sustainable industrial applications. To date, substantial research advancements are achieved in catalyst design for laboratory‐based water electrolysis. While the designed catalysts demonstrate remarkable performance at laboratory‐based low current densities, they suffer from marked deteriorations in both activity and long‐term stability under industrial‐level high‐current‐density operations. To provide a timely assessment that helps bridge the gap between laboratory‐scale fundamental research and industrial‐scale practical water electrolysis technology, here the current advancements in various commercial water electrolyzers are first systematically analyzed, then the key parameters including work temperature, current density, lifetime of stacks, cell efficiency, and capital cost of stacks are critically evaluated. In addition, the impact of high current density on the electrocatalytic behavior of catalysts, including intrinsic activity, long‐term stability, and mass transfer, is discussed to advance the catalyst design. Therefore, by covering a range of critical issues from fundamental material design principles to industrial‐scale performance parameters, here the future research directions in the development of highly efficient and low‐cost catalysts are presented and a procedure for screening laboratory‐designed catalysts for industrial‐scale water electrolysis is outlined.

Heterogeneous Catalysis in the Synthesis of Nitrogen‐Containing Heterocyclics

AbstractThe synthesis of nitrogen‐containing heterocyclic compounds using heterogeneous catalysis is a topic of significant interest in organic synthesis and chemical research. Heterogeneous catalysis offers several advantages over homogeneous catalysis, including easier separation and recovery of the catalyst, reduced waste generation, and potentially higher stability and reusability. In this review, the pivotal role of heterogeneous catalysis in synthesizing nitrogen‐containing heterocyclic compounds is explored. Various types of heterocycles and the specific applications of these compounds in drug discovery and material development are discussed in detail. This review discusses various examples of heterogeneous catalysts employed in the synthesis of nitrogen‐containing heterocycles, including metal oxides, supported metals, metal nanoparticles, zeolites, and other porous materials. Emphasis is placed on the mechanistic insights and reaction pathways facilitated by different catalysts. Additionally, recent advancements and innovations in the field are discussed, including novel catalyst designs, green chemistry approaches, and emerging trends in catalytic materials. The aim is to provide a comprehensive overview of the impact and potential of heterogeneous catalysis in this important area of organic synthesis.

One-pot Hydrogenolysis of Polyethylene Terephthalate (PET) to p-xylene over CuZn/Al2O3Catalyst.

Chemical upcycling of plastic wastes into valuable chemicals is a promising strategy for resolving plastic pollution, but economically viable methods currently are still lacking. Here, we report one-pot hydrogenolysis of PET plastic into p-xylene with an excellent yield (99.8 %) over a robust non-precious Cu-based catalyst, CuZn/Al2O3, in the absence of alcohol solvents. The presence of Zn species promotes the dispersion of Cu0 and increases the ratio of Cu+/Cu0, whereas the synergistic effect of Cu0 and Cu+ leads to a superior performance in the conversion of PET. The combination of GC-MS, 13C CP MAS NMR, 2D 1H-13C CP HETCOR NMR spectroscopy and kinetic studies for the first time demonstrates 4-methyl benzyl alcohol as an important reaction intermediate in the hydrogenolysis of PET. Mechanistic studies indicate that the conversion of PET mainly follows a hydrogenolysis process, involving the cleavage of ester bonds to alcohols and the C-O bond cleavage of alcohols to alkanes. This work not only brings new insight for understanding the upgrading pathway of PET, but also provides a guidance for the design of high-performance non-precious catalysts for the chemical upcycling of plastic wastes.